Method of manufacture of luminescent materials



Patented F eb. 14, 1950 JI I 40 um'rso STATES PATENT oFFicE METHOD or MAKIUFACTURE or LpMiNEsosNr MATERIALS James H; Schulman, Cambridge, Mass, assignor to Sylvania'Electric Products In'c., Salem, Mass., I v a corporation of Massachusetts No Drawing. .Application Matti; 28, 1946,

Serial No. 657,922

l 8Claims. (01. 252 30110 This invention relates to luminescent mamixture of a calcium salt and a manganese salt terials and more particularly to phosphors used with silicic acid in the presence of the vapor of in the preparation of a coating of fluorescent maa lead compound. This lead-bearing vapor may terial for an electric gaseous discharge device, he produced in the firing chamber by placing such as a fluorescent lam'p. therein a separate vessel containing a suitable An object of this invention is to provide a, flulead compound. Alternatively, the activator orescent material of fine and uniform particle compound 'may be disposed in the bottom of a size. suitable container and the phosphor charge piled .Another object is toprovide a fluorescent maon top of it or it may be disposed on top of the terial which, when applied to a lamp, will proll phosphor charge. If desired, a blend of a calvide. the lamp with a coating which will maintain cium and a manganese compound with silicic acid good brightness throughout the life of the lamp. can be prefired to give CaMnSiOs which is, inert Afurther object is to provide afiuorescent mato 2537 A. U. radiation. This fired material terial which, when applied to alamp, will promay then be further heated in the vapor of a t me the lamp with a smooth even coating. suitable lead compound, whereupon lead enters Further objects, advantages and features will t Structure and forms t r 310 Phos- I -appare t f t following p fi a on. phor which fluoresces pink under 2537 A. U.

In the preparation of certain luminescent maexcitation. v terials i h been the pralltice 170 add an acti- The amount of the activator which enters the vator such as lead in order to obtain a product phosphor may be controlled by the temperature which will fluoresce under 2537 A. U. excitation. and time of firin and by t Choice of t-,1; It has also been the practice, in 501119081568, in yator compounds of diiferent vapor pressures. preparing lummescent materials to ut1l1Ze a flux AS suitable lead compounds I have used lead or catalyst to accelerate the reaction of phosphor fl oride lead dioxide, lead monoxide and m synthesis. In both of these cases the activator 2v chloride but any other lead compounds g v and/Or the catalyst have usually been mixed as a a sufiicient concentration of lead-bearing vapor solid with the phosphor charge. In'the case of a the firing temperatures employed are Satis the activator. many activator compounds fuse at factory. I have found 2100 F. to be a satisfac comparatively l temperatures before any tory firing temperature. Thus an activator can stantial reaction. takes place with the phosphor be added to a raw material blend or a finished ingredients. This 'sintering is undesirable bephosphor by this method cause it causes the final phosphor product to be characterized by larger particle sizes than are I ,12 1; 23??? ggg nigo $3 desired. When a catalyst is mixed as a solid prpfired CaMnSiOg in f and i g with the phosphor charge it has been found that i lead com ound 1 another 0 I th sometimes the stimulated reaction of the fluoput thse g g S in n rum fi rescent material does not take place uniformly I b th 1 d e a b i throughout the entire mass, some particles of the F1 erhwl e compound W B on 0D fluorescent material reacting slower than others. 0 e p osphor chalge The crumbles are then Themethod Of my invention embodies the idea f when the temperature pf introducing the activator and/or the catalyst z es pom Where lead compound starts into the phosphor charge in a vapor state instead 0 Vaponze lead'bearmg Vapor permeates the of nliixirigtin the activator and/ or the catalyst in 2 5 1 iz i ig gi gfi l igi ;312: 333

so id s a e. -I have found that when thisvis done :intering of the phosphor is avoided and finer highty satisfactqry in the Preparation of a 9 particle Sizes are obtainable; and n the caseof pension of luminescent material to be applied the catalyst, the reaction of the fluorescent ma- P the Walls of a glass tube to be manufactured teriaycompound is sti ulatednifo l -th h into a fluorescent lamp, because a finer particle the entire mass,-all particles appearing to react Size and a lower powder Weight is thereby at a more u if rate i510 tained. The lower powder weight reduces manufacturing costs and the finer particle size provides'a smoother coating on the lamp.

The process which I have employed insyn- The. principle of vapor-phase activators may thesizing an activated- :phosphor, sucl'ilas calcium beextended to activators other thanlead without leadi silicate, lforlzexample, comprises firinga departing from the spirit of the invention.

Catalysts The action of catalysts in promoting solid state reactions is well known. Such agents have been used in the synthesis of sulfide and silicate phosphors. In both cases the catalyst has usually been mixed as a solid with the material to be reacted. With reference to catalyst-accelerated silicate reactions, a theory has been advanced that the catalyst dissolves away a barrier layer of reacted silicate, thus uncovering the underlying unreacted metal oxides which can further react.

In the method of my invention volatile fluxing agents are not admixed as a solid with the phosphor charge but their vapors alone are suflicient to adequately accelerate the reaction of phosphor synthesis. A flux, such as cadmium chloride, may be placed in the bottom of a firing vessel and the phosphor blend to be fired piled on top of it or it may be disposed on top of the phosphor blend. Alternatively, the phosphor mix and the flux may be disposed in separate containers, so long as the flux vapor has good access to the phosphor charge. Since the vapors alone perform the catalysis, this action is different from that normally ascribed to fluxes, the vapors not being able to dissolve any barrier layer of silicate.

I have found the above-mentioned process extremely satisfactory in the synthesis of manganese-activated silicate phosphor when one of the volatile halides is used as a fiuxing agent. For example, I have prepared zinc ortho-silicate activated with manganese by firing a dry blend of ZnO, MnCOa and S102 in the presence of a volatile halide such as CdCl2, ZnClz, PbClz, and HgCl. This method has also been found advantageous in the preparation of zinc beryllium silicate activated with manganese, magnesium orthosilicate activated with manganese and cadmium silicate activated with manganese when the dry blend of the phosphor charge is fired in the presence of a volatile halide, such as one of the halide compounds mentioned above for example.

The fiuxing agent may be placed in a container separate from the container in which the phosphor charge is disposed or it may be placed in the bottom of the same vessel in which the phosphor charge is fired. Although it is possible to fire the materials in open containers where no provision is made to prevent escape of the flux vapor it is not the preferred method. Preferably provision should be made to prevent the escape of the volatilized material by firing the charge in a closed container.

The principle of vapor-phase catalysts may also be extended to sulfide and other type phosphors without departing from the spirit of the invention.

What I claim is:

1. The process of preparing a manganese activated silicate phosphor selected from the group consisting of zinc orthosilicate, zinc beryllium silicate, magnesium orthosilicate, cadmium silicate and calciiun silicate which comprises disposing the components thereof, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing at least one compound selected from the group consisting of CdClz, ZnClz, HgCl, PbClz, PbFz, PbO, and PbOz, in the solid state, in said chamber, physically separate from said components but in close proximity thereto; and heating said components and said compound to a temperature high enough to vaporize said compound and cause said vapors to permeate the solid state components of said phosphor.

2. The process of preparing a manganese activated calcium silicate phosphor which comprises disposing a blend of CaCOa, MnCOa, and SiOz, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing at least ongcompound selected from the group consisting of CdClz, ZnClz, HgCl, PbClz, PbFz, PhD, and PbO2, in the solid state, in said chamber physically separate from said blend but in close proximity thereto; and heating said blend and said compound to a temperature high enough to vaporize said compound and cause said vapors to permeate the solid state blend of said phosphor.

3. The process of preparing a manganese activated silicate phosphor selected from the group consisting of zinc orthosilicate, zinc beryllium silicate, magnesium orthosilicate, cadmium silicate and calcium silicate which comprises disposing the components thereof, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing lead oxide in the solid state, in said chamber physically separate from said components but in close proximity thereto; and heating said components and said lead oxide to a temperature high enough to vaporize said lead oxide and cause said vapors to permeate the solid state components of said phosphor.

4. The process of preparing a manganese activated calcium silicate phosphor which comprises disposing a blend of CaCOx, MnCOs and $102, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing lead oxide in the solid state, in said chamber physically separate from said blend but in close proximity thereto; and heating said blend and said lead oxide to a temperature high enough to vaporize said lead oxide and cause said vapor to permeate the solid state blend of said phosphor.

5. The process of preparing a manganese activated silicate phosphor selected from the group consisting of zinc orthosilicate, zinc beryllium silicate, magnesium, orthosilicate, cadmium silicate and calcium silicate which comprises disposing the components thereof, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing PbClz in the solid state, in said chamber, physically separate from said components but in close proximity thereto; and heating said components and said PbC12 to a temperature high enough to vaporize said PbCl2 and cause said vapors to permeate the solid state components of said phosphor.

6. The process of preparing a manganese activated calcium silicate phosphor which comprises disposing a blend of CaCO3, MDCO: and SiOz, in the solid state, in the proportions necessary to form the phosphor in an enclosed chamber; disposing PbCh in the solid state, in said chamber physically separate from said blend but in close proximity thereto; and heating said blend and said PbClz to a temperature high enough to vaporize said PbCh and cause said vapor to permeate the solid state blend of said phosphor.

7. The process of preparing a manganese activated silicate phosphor selected from the group consisting of zinc orthosilicate, zinc beryllium silicate, magnesium orthosilicate, cadmium silicate and calcium silicate which comprises disposing the components thereof, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing PbFi 5 in the solid state, in said chamber, physically separate from said components but in close proximity thereto; and heating said components and said PbFz to a temperature high enough to vaporize said PbFz and cause said vapors to permeate the solid state components of said phosphor.

8. The process of preparing a manganese activated calcium silicate phosphor which comprises disposing a blend of CaCOa, MnCOs, and S102, in the solid state, in the proportions necessary to form the phosphor, in an enclosed chamber; disposing PbFz in the solid state, in said chamber physically separate from said blend but in close proximity thereto and heating said blend and said PbFz to a temperature high enough to vaporize said PbFz and cause said vapor to permeate the solid state blend of said phosphor.

JAMES H. SCHULMAN.

REFERENCES CITED The following references are of record in the file of :this patent:

UNITED STATES PATENTS Number Name Date 1,954,691 De Boer Apr. 10, 1934 2,124,225 Batchelor July 19, 1938 2,238,926 Moore Apr. 8, 1941 2,247,192 Fonda June 24, 1941 2,254,956 Aschermann Sept. 2, 1941 2,299,510 Steadman Oct. 20, 1942 Leverenz Feb. 22, 1949 

1. THE PROCESS OF PREPARING A MANAGEMENT ACTIVATED SILICATE PHOSPHOR SELECTED FROM THE GROUP CONSISTING OF ZINC ORTHOSILICATE, ZINC BERYLIUM SILICATE, MAGNESIUM ORTHOSILICATE, CADMIUM SILICATE AND CALCIUM SILICATE WHICH COMPRISES DISPOSING THE COMPONENTS THEREOF, IN THE SOLID STATE, IN THE PROPORTIONS NECESSARY TO FORM THE PHOSPHOR, IN AN ENCLOSED CHAMBER; DISPOSING AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF CDCL2, ZNCL2, HGC1, PBCL2, PBF2, PBO, AND PBO2, IN THE SOLID STATE, IN SAID CHAMBER, PHYSICALLY SEPARATE FROM SAID COMPONENTS BUT IN CLOSE PROXIMITY THERETO; AND HEATING SAID COMPONENTS AND SAID COMPOUND TO A TEMPERATURE HIGH ENOUGH TO VAPORIZE SAID COMPOUND AND CAUSE SAID VAPORS TO PERMEATE THE SOLID STATE COMPONENTS OF SAID PHOSPHOR. 